CN110212201A - Battery core, battery pole piece and preparation method thereof, battery - Google Patents
Battery core, battery pole piece and preparation method thereof, battery Download PDFInfo
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- CN110212201A CN110212201A CN201910512035.6A CN201910512035A CN110212201A CN 110212201 A CN110212201 A CN 110212201A CN 201910512035 A CN201910512035 A CN 201910512035A CN 110212201 A CN110212201 A CN 110212201A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention relates to a kind of battery cores, battery pole piece and preparation method thereof, battery, wherein, battery core, the first cathode pole piece of two panels, the anode pole piece between the first cathode pole piece described in two panels including being located at outside, and the diaphragm between first cathode pole piece and the anode pole piece；First cathode pole piece includes the first negative current collector, the negative electrode active material coating on one surface of the first negative current collector, and the flame retardant coating on another surface of the first negative current collector, the negative electrode active material coating on each first cathode pole piece are oppositely arranged with the anode pole piece；Wherein, the raw material of the flame retardant coating includes fire retardant, antisettling agent, bonding agent and surfactant.The present invention is by the flame retardant coating on the first cathode pole piece, and the flame-retardant layer is located at the outermost of battery core, can be improved the security performance of battery, and will not influence the chemical properties such as the internal resistance of cell and multiplying power, circulation.
Description
Technical field
The present invention relates to battery technology fields, more particularly to a kind of battery core, battery pole piece and preparation method thereof, battery.
Background technique
In recent years, the fields such as portable electronic product, electric car, energy-accumulating power station are fast-developing, and lithium ion battery is because of it
Energy density is high, operating voltage is high, self discharge is small, the advantages that having extended cycle life is as preferred electrochmical power source.With product
Upgrading, people are higher and higher to the energy density requirement of lithium ion battery, but security performance but upgrades without synchronous, in reality
In use process, safety accident happens occasionally, this is mainly due to lithium ion battery by high temperature, the processes septation such as fall
Contraction, embrittlement cause cathode and anode contact short circuit etc. to generate thermal runaway, cause battery catches fire and even explode, seriously affect user's
Safety of life and property.For the power battery bigger for capacity, security performance is even more important.
In order to promote the security performance of lithium ion battery, some technologies are by adjusting electrolyte prescription, in the electrolytic solution
Adding fire retardant, overcharging additive etc. improves security performance.But such way often sacrifices the chemical property of battery, no
It can tackle the problem at its root.It is that battery afflux liquid is divided into two regions there are also technology, a region applies wherein
Cover active material coating, another region is coated with ptc material coating, when short circuit occurs in battery or overcharging equal high temperatures and increases,
The resistivity of ptc material increases rapidly, to block the transmission of electrolyte ion, or circuit is directly blocked, to play protection
The effect of battery system promotes the security performance of battery, although this method prevent to a certain extent battery temperature into one
Step increases, but it is easy to cause the raising of the internal resistance of cell, reduction of battery energy density etc., influences on the performance of battery very big.
It is fire retardant to be wrapped in microcapsules, then mix with containing the protectant solution of diaphragm and be coated on diaphragm there are also some technologies
Microcapsules are finally fixed on membrane surface by surface, and when thermal runaway occurs for battery, release resistance fire retardant protects battery
Shield, however such method will increase the internal resistance of diaphragm, influence lithium ion transport, the high rate performance and cryogenic property to battery generate
Adverse effect.
Summary of the invention
Based on this, it is necessary to provide a kind of battery core, the security performance of battery can be improved well, and will not influence battery
Internal resistance and chemical property.
A kind of battery core, including being located at first cathode pole piece of two panels in outside, being located between the first cathode pole piece described in two panels
Anode pole piece, and the diaphragm between first cathode pole piece and the anode pole piece；
First cathode pole piece includes the first negative current collector, bearing on one surface of the first negative current collector
Pole active material coating, and the flame retardant coating on another surface of the first negative current collector, each first cathode
The negative electrode active material coating on pole piece is oppositely arranged with the anode pole piece；Wherein, the raw material of the flame retardant coating
Including fire retardant, antisettling agent, bonding agent and surfactant.
In one embodiment, the battery core further includes the second cathode pole piece, and second cathode pole piece includes the second cathode
Collector and the negative electrode active material coating being respectively arranged on two surface of the second negative current collector；
The quantity of the anode pole piece is m, and m is the integer more than or equal to 2；The quantity of second cathode pole piece is m-
1；
Second cathode pole piece described in anode pole piece described in m piece and m-1 piece is arranged alternately, and the adjacent anode pole piece and
Diaphragm is equipped between second cathode pole piece.
The fire retardant is selected from least one of inorganic fire retardants and organic fire-retardant in one of the embodiments,；
Wherein, the inorganic fire retardants is selected from encapsulated red phosphorus, polyphosphoric acid amine, melamine polyphosphate expansion type flame retardant
At least one of with composite inorganic flame retardant；The organic fire-retardant is selected from 2,2- bis- ((4- Phenoxyphenyl phosphine oxides)-
P-aminobenzoic acid) propane, bis- (2- carboxy ethyl) phosphonic acids, double-(p- benzoic acid)-phenyl-phosphamide, N- benzoic acid-(second
Base-N- benzoic acid formamide) phosphamide, poly- N- aniline-phenyl-phosphamide, -4,6 (p-aminophenyl of 2- (Dimethyl phosphate)
Formic acid)-s-triazine, high fluorine carbonic ester, phosphate flame retardant, six benzene oxygen rings, three phosphonitrile, the miscellaneous -10- phospha of 9,10- dihydro-9-oxy
At least one of phenanthrene -10- oxide and phosphine esters fire retardant.
Encapsulated red phosphorus refers to using ultra-fine Wrapped up Phosphorus Fire Retardant made of coating technology；Composite inorganic fire retardant refer to by
The nothing of at least two compositions in aluminium hydroxide, magnesium hydroxide, red phosphorus, ammonium polyphosphate, zinc borate, antimony oxide and molybdenum compound etc.
Machine fire retardant.
The fire retardant is the mixture of inorganic fire retardants and organic fire-retardant in one of the embodiments,.
The bonding agent is selected from aqueous styrene-butadiene latex, Kynoar, carboxymethyl cellulose in one of the embodiments,
At least one of sodium, polytetrafluoroethylene (PTFE) and polyethylene glycol oxide；And/or
The antisettling agent is selected from nonionic polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty acid sulfate and poly- two
At least one of alcohol ether；And/or
The surfactant is selected from alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxy second
At least one of olefin(e) acid, fatty acid methyl ester ethoxylate and ethylene oxide adduct of polypropylene glycol.
Yet another object of that present invention is to providing a kind of battery pole piece, including collector, it is set on one surface of collector
Active material coating, and the flame retardant coating on another surface of the collector；The raw material of the flame retardant coating includes
Fire retardant, antisettling agent, bonding agent and surfactant.
Yet another object of that present invention is to provide a kind of preparation method of battery pole piece, comprising the following steps:
Collector is provided；
Active material coating is coated on one surface of collector, forms active material coating；
The raw material of flame retardant coating is uniformly mixed with solvent, obtains anti-flaming dope, the anti-flaming dope is coated in described
On another surface of collector, after dry, the flame retardant coating is formed；The raw material of the flame retardant coating includes fire retardant, anti-settling
Agent, bonding agent and surfactant.
In one of the embodiments, in the step that the raw material by flame retardant coating is uniformly mixed with solvent, first will
The solvent, the antisettling agent, the bonding agent and surfactant mixing stir evenly, and it is mixed to obtain the first mixing；Again will
First mixed liquor and fire retardant mixing, stir evenly under vacuum conditions.
The fire retardant, the solvent, the antisettling agent, the bonding agent and described in one of the embodiments,
The weight ratio of surfactant is (6.5~8.9): (5.8~7.7): (0.05~0.08): (0.03~0.09): (0.005~
0.01)；
The solvent is selected from least one of dimethyl carbonate, deionized water, N-Methyl pyrrolidone.
Another object of the present invention is to provide a kind of battery, and the battery includes above-mentioned battery core.
The invention has the following advantages:
1) battery core of the invention, by being arranged the first cathode pole piece, and the first cathode pole piece far from anode pole piece one
Face is equipped with flame retardant coating and (is substituted for the negative electrode active material coating being located on outermost layer cathode pole piece in traditional battery core above-mentioned
Flame retardant coating), which is uniformly coated on afflux by each raw material component collocation, and heat occurs in the inside of battery core and loses
When control, the flame retardant coating on the first cathode pole piece can play flame retardant effect in time, prevent inside battery because temperature further increases
And the burning occurred, improve the security performance of battery；Do not join moreover, because being located at the folded outermost negative electrode active material coating of core
The negative electrode active material coating on outermost layer cathode pole piece is therefore substituted for above-mentioned resistance with the electrochemical reaction of inside battery
Coating is fired, will not influence the chemical properties such as internal resistance, energy density, capacity, cycle performance and the multiplying power of battery.
2) compound with diaphragm etc. traditional compared to the fixation position that fire retardant is coated in every battery pole piece or by it
A table of first cathode pole piece far from anode pole piece for being not involved in battery chemistries reaction is arranged in flame retardant coating by method, the present invention
On face, will not influence inside battery anode and cathode active materials coating has effective affecting acreage, will not influence lithium ion in electricity
Transmission inside pond, therefore, the present invention can will not influence the electrochemistry of battery while improving the security performance of battery
Energy.
3) preparation method simple process of the invention is easily achieved, and is not required to be transformed existing equipment adjustment substantially, together
When, additionally it is possible to the cost of battery manufacture is reduced, a wide range of promote is suitable for.
Detailed description of the invention
Fig. 1 is the longitudinal section cut-away view of the battery pole piece of an embodiment of the present invention；
Fig. 2 is the longitudinal section cut-away view of the battery core of an embodiment of the present invention；
Fig. 3 is the longitudinal section cut-away view of the anode pole piece of battery core in Fig. 2；
Fig. 4 is the longitudinal section cut-away view of the second cathode pole piece of battery core in Fig. 2；
Fig. 5 is the longitudinal section cut-away view of the battery core of comparative example 1 of the present invention；
Fig. 6 is the longitudinal section cut-away view of the battery core of comparative example 2 of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
An embodiment of the present invention provides a kind of battery pole piece 10, as shown in Figure 1, including collector 11 and being set to collector
Active material coating 12 on 11 1 surfaces, and the flame retardant coating 13 on another surface of collector 11.Wherein, fire-retardant painting
The raw material of layer 13 includes fire retardant, antisettling agent, bonding agent and surfactant.
In one embodiment, collector 11 with a thickness of 4 μm~12 μm.
Collector refers to the structure or part for collecting electric current, concretely metal foil, such as aluminium foil, copper foil.
In this embodiment, the collector 11 of battery pole piece 10 is copper foil, and the raw material of active material coating 12 is negative
Pole active material coating, negative electrode active material coating is by including the raw material of graphite, conductive agent, bonding agent and auxiliary agent through being homogenized process
It is made.
Another embodiment of the present invention provides a kind of preparation method of above-mentioned battery pole piece, comprising the following steps:
S1, collector is provided.
In this embodiment, collector is copper foil.It is appreciated that in other embodiments, collector can be it
The collector of his material.
S2, active material coating is coated on a surface of collector, form active material coating.
In this embodiment, active material coating is negative electrode active material coating.
Specifically, graphite, conductive agent, bonding agent and auxiliary agent are mixed, and negative electrode active material is made by homogenate technique
Then negative electrode active material coating is coated on a surface of collector using coating machine, is dried by continuous baking oven by coating
Afterwards, active material coating is formed.
S3, the raw material of flame retardant coating is uniformly mixed with solvent, obtains anti-flaming dope, applied on another surface of collector
Anti-flaming dope made of step S3 is covered, after dry, forms flame retardant coating.Wherein, the raw material of flame retardant coating includes fire retardant, resists and sink
Depressant prescription, bonding agent and surfactant.
Specifically, anti-flaming dope is coated on another surface of collector using coating machine, is dried by continuous baking oven
Afterwards, flame retardant coating is formed.
It should be understood that above-mentioned steps S2 and S3 not stringent sequence requirement, step S2 or first can be first carried out
Step S3 is carried out, the operation of step S2 and step S3 can also be carried out simultaneously.
In one embodiment, in the step for being uniformly mixed the raw material of flame retardant coating with solvent, first by solvent, anti-settling
Agent, bonding agent and surfactant mixing stir evenly, and it is mixed to obtain the first mixing；The first mixed liquor and fire retardant are mixed again, true
It is stirred evenly under empty condition.
In one embodiment, the vacuum degree of vacuum condition is -70KPa~-90KPa.
Further, stirring is stirred using blender, and the revolution speed of blender is 10r/min~15r/min, from
Turn 300r/min~800r/min.
Specifically, first solvent, antisettling agent, bonding agent and surfactant are added in blender, with the 10r/min that revolves
~15r/min, rotation 300r/min~800r/min stir 30min~150min, then fire retardant is added into blender, take out true
After empty extremely -70KPa~-90KPa, continues to stir 30min~210min with same rotational speed, obtain evenly dispersed anti-flaming dope.
In one embodiment, fire retardant is selected from least one of inorganic fire retardants and organic fire-retardant.Wherein, inorganic resistance
Agent is fired in encapsulated red phosphorus, polyphosphoric acid amine, melamine polyphosphate expansion type flame retardant and composite inorganic flame retardant
It is at least one；Organic fire-retardant be selected from bis- ((the 4- Phenoxyphenyl phosphine oxide)-p-aminobenzoic acid) propane (BPOAP) of 2,2-,
Bis- (2- carboxy ethyl) phosphonic acids, double-(p- benzoic acid)-phenyl-phosphamide (BCNPO), N- benzoic acid-(ethyl-N- benzoic acid
Formamide) phosphamide (BNPPO), poly- N- aniline-phenyl-phosphamide (PDPPD), 2- (Dimethyl phosphate) -4,6 be (to amino
Benzoic acid)-s-triazine (DPTPO), high fluorine carbonic ester, phosphate flame retardant (HBDP), six benzene oxygen rings, three phosphonitrile, 9,10- dihydro-
At least one of 9- oxa- -10- phospho hetero phenanthrene -10- oxide (DOPO) and phosphine esters fire retardant etc..
In one embodiment, fire retardant is the mixture of inorganic fire retardants and organic fire-retardant.
In this way, being acted on by inorganic fire retardants and organic fire-retardant collocation, the flame retardant effect of flame retardant coating is improved.Compared with
Excellently, fire retardant is the mixture of three phosphonitrile of ammonium polyphosphate and six benzene oxygen rings.
Further, the mass ratio of ammonium polyphosphate and six benzene oxygen rings, three phosphonitrile is (2.5~4): (4~6).
In one embodiment, solvent selects at least one of dimethyl carbonate, deionized water and N-Methyl pyrrolidone.
In one embodiment, bonding agent is selected from aqueous styrene-butadiene latex (SBR), Kynoar (PVDF), carboxymethyl cellulose
At least one of plain sodium (CMC), polytetrafluoroethylene (PTFE) (PFTE) and polyethylene glycol oxide (PEO).
In one embodiment, antisettling agent is selected from nonionic polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty acid sulphur
At least one of hydrochlorate (Uniperol W) and polyglycol ether.
In one embodiment, surfactant is nonionic surface active agent.
Specifically, surfactant alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, aliphatic acid polyethenoxy
At least one of acid, fatty acid methyl ester ethoxylate and ethylene oxide adduct of polypropylene glycol.
In one embodiment, the weight ratio of fire retardant, solvent, antisettling agent, bonding agent and surfactant be (6.5~
8.9): (5.8~7.7): (0.05~0.08): (0.03~0.09): (0.005~0.01).
In one embodiment, by weight, the raw material of anti-flaming dope includes 65~89 parts of fire retardants, 58~77 parts of carbonic acid
Dimethyl ester, 0.5~0.9 part of polyglycol ether, 0.3~0.9 part of aqueous styrene-butadiene latex and 0.05~0.1 part of alkylphenol-polyethenoxy
Ether, wherein fire retardant includes three phosphonitrile of ammonium polyphosphate and six benzene oxygen rings, and ammonium polyphosphate and the weight ratio of six benzene oxygen rings, three phosphonitrile are
(2.5~4): (4~6).
Further, ammonium polyphosphate and the weight ratio of six benzene oxygen rings, three phosphonitrile are 3:5.
In one embodiment, the preparation method of battery pole piece further include to formed protect liquid coating after coiled material carry out roll-in,
Slitting and crosscutting step.
Another embodiment of the present invention provides a kind of battery core, as shown in Fig. 2, battery core 100 includes the two panels the positioned at outside
One cathode pole piece 110, at least a piece of anode pole piece 120 between first cathode pole piece of two panels, and it is negative positioned at first
Diaphragm 130 between pole pole piece 110 and anode pole piece 120.
Wherein, the first cathode pole piece 110 includes the first negative current collector 111, is respectively coated on the first negative current collector phase
Negative electrode active to the negative electrode active material coating 112 and flame retardant coating 113 on two surfaces, on each first cathode pole piece 110
Material coating 112 is oppositely arranged with anode pole piece 120；Wherein, the raw material of flame retardant coating 113 include fire retardant, antisettling agent,
Bonding agent and surfactant.
Specifically, the first cathode pole piece 110 is the battery pole piece 10 that above-mentioned collector is copper foil, or use above method system
Standby obtained battery pole piece.
As shown in figure 3, anode pole piece 120 includes plus plate current-collecting body 121 and is respectively arranged on plus plate current-collecting body 121 two relatively
Surface on positive electrode active materials coating 122.
Diaphragm 130 is selected from least one of double-surface ceramics and single side ceramic diaphragm.
Diaphragm 130 includes basement membrane (not shown) and is set to epilamellar ceramic coating (not shown), and wherein basement membrane is PE (poly-
Ethylene) film or PP (polypropylene) film, the porosity of basement membrane is 35%~60%, basement membrane with a thickness of 9 μm~20 μm.
In one embodiment, battery core 100 further includes the second cathode pole piece 140.As shown in figure 4, the second cathode pole piece 140 wraps
Including second negative current collector 141 and the negative electrode active material that is respectively arranged on 141 two opposite surfaces of the second negative current collector
Coating 142.
Specifically, the quantity of the first cathode pole piece 110 is 2, and the quantity of anode pole piece 120 is n, and n is more than or equal to 2
Integer；The quantity of second cathode pole piece 140 is n-1；N piece anode pole piece 120 and the second cathode pole piece of n-1 piece 140 alternate
Arrangement, and diaphragm 140 is equipped between adjacent anode pole piece 120 and the second cathode pole piece 140.
Specifically, by the first above-mentioned cathode pole piece, anode pole piece, the second cathode pole piece and diaphragm by the way of lamination
It is assembled and is encapsulated, obtain battery core.
Wherein, lamination is to carry out the first cathode pole piece, anode pole piece, the second cathode pole piece on laminating machine by diaphragm
Assembling.
Another embodiment of the present invention provides a kind of battery comprising above-mentioned battery core 100.
Specifically, the battery core that above-mentioned assembled and encapsulation obtains the processes such as fluid injection, infiltration, chemical conversion, partial volume are carried out to be made
Battery.
Wherein, the main component of electrolyte used in fluid injection is PC (polycarbonate), DMC (dimethyl carbonate), EC (carbonic acid
Vinyl acetate), EMC (methyl ethyl carbonate), LiPF6(lithium hexafluoro phosphate) etc..
The following are specific embodiments
Embodiment 1
1, the preparation of negative electrode active material coating
By graphite, conductive black, sodium carboxymethylcellulose, aqueous styrene-butadiene latex SBR and deionized water according to mass ratio
91.5:6:1.2:1.3:102 is added in batches in homogenate blender, and addition sequence is followed successively by deionized water, carboxymethyl cellulose
Sodium, conductive black, graphite and aqueous styrene-butadiene latex SBR are added before graphite with the 15r/min that revolves, rotation 300r/min stirring
300min is added after graphite with the 15r/min that revolves, rotation 800r/min, stirs 150min under the conditions of vacuum degree is -85KPa,
After homogenate, finely dispersed negative electrode active material coating is obtained, coating is placed in transfer tank, and stir with 15r/min low speed
It mixes, it is spare.
2, the preparation of anti-flaming dope
It is by weight that 3:5 is compounded and hindered by inorganic fire retardants ammonium polyphosphate and six benzene oxygen ring of organic fire-retardant, three phosphonitrile
Agent is fired, then presses the fire retardant, dimethyl carbonate, polyglycol ether, aqueous styrene-butadiene latex SBR and alkyl phenol polyoxyethylene ether
Mass ratio 7.8:5.9:0.05:0.09:0.005 is successively added in homogenate blender and mixes.Specifically addition sequence are as follows: first by carbon
Dimethyl phthalate, polyglycol ether, aqueous styrene-butadiene latex SBR and alkyl phenol polyoxyethylene ether are added in blender, with the 10r/ that revolves
Min, rotation 300r/min stir 35min, then ammonium polyphosphate and six benzene oxygen rings, three phosphazene composition are added into blender, take out true
After empty extremely -90KPa, continues to stir 210min with same rotational speed, after obtaining evenly dispersed anti-flaming dope, coating is placed in transfer
Tank, and stirred at low speed with 15r/min, it is spare.
3, the preparation of battery pole piece
Above-mentioned negative electrode active material coating is first coated on to the side of copper foil of affluxion body with coating machine, is dried by continuous baking oven
After dry, by the other side of anti-flaming dope coating and copper foil, the coiled material for completing coating after drying carries out roll-in, slitting and cross cutting,
It is negative electrode active material coating, the first cathode pole piece that another side is flame retardant coating on one side.
Above-mentioned negative electrode active material coating is respectively coated with coating machine in the two sides of copper foil of affluxion body, by continuous baking oven
After drying, the second cathode pole piece that two surfaces are equipped with negative electrode active material coating is obtained.
Lithium battery anode reactive coating is respectively coated with coating machine in the two sides of current collector aluminum foil, is dried by continuous baking oven
After dry, the anode pole piece that two surfaces are equipped with positive electrode active materials coating is obtained.
4, the preparation of battery core and battery
First negative electrode tab, the second negative electrode tab and anode pole piece are assembled on automatic laminating machine by diaphragm, obtained
Battery core as shown in Figure 2.Diaphragm used is double-surface ceramics diaphragm, basement membrane PE, porosity 45%, with a thickness of 9 μm, positive pole
The quantity of piece is 15, and the quantity of the first cathode pole piece is 2, and the quantity of the second negative electrode tab is 15, and the sequence of lamination is the 1st layer and is
First cathode pole piece, the 2nd~30th layer is alternately stacked for anode pole piece and the second cathode pole piece, and the 31st layer is the first negative electrode tab,
Wherein the 1st layer and the 31st the first negative electrode tab be equipped with negative electrode active material coating one side respectively with the 2nd layer and the 30th layer just
Pole pole piece is opposite, and is spaced apart by diaphragm between adjacent pole piece.
After the completion of battery core preparation, fire-retardant soft bag lithium ionic cell is made using processes such as encapsulation, fluid injection, chemical conversion, partial volumes.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that fire retardant in 2 anti-flaming dope of embodiment, solvent, anti-
The mass ratio of sedimentation agent, bonding agent and surfactant is 6.5:7.7:0.05:0.05:0.005.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that when embodiment 3 prepares anti-flaming dope, each component is same
When be added in blender, then with the 10r/min that revolves, rotation 300r/min stirs 245min, and when being up to 35min in stirring
Vacuum is opened, and vacuum degree is same as Example 1.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, and difference from Example 1 is, the fire retardant in anti-flaming dope is poly-
Ammonium phosphate.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, and difference from Example 1 is, the fire retardant in anti-flaming dope is six
Three phosphonitrile of benzene oxygen ring.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that the fire retardant in anti-flaming dope be inorganic fire retardants and
The combination of organic fire-retardant, wherein inorganic fire retardants is encapsulated red phosphorus, organic fire-retardant 2, bis- ((the 4- Phenoxyphenyl oxygen of 2-
Change phosphine)-p-aminobenzoic acid) propane (BPOAP), it should be noted that the mass ratio of inorganic fire retardants and organic fire-retardant with
Embodiment 1 is identical.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that the fire retardant in anti-flaming dope be inorganic fire retardants and
The combination of organic fire-retardant, wherein inorganic fire retardants is melamine polyphosphate, organic fire-retardant 9,10- dihydro-9-oxy
Miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO), it should be noted that the mass ratio and reality of inorganic fire retardants and organic fire-retardant
It is identical to apply example 1.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that, the number of the first cathode pole piece in the battery core of comparative example 1
Amount is 1, and in addition a piece of first cathode pole piece is substituted with the second cathode pole piece.Specifically, in comparative example 1 lamination sequence are as follows: the 1st
Layer is the first cathode pole piece, and the 2nd~31st layer is alternately stacked for anode pole piece with the second cathode pole piece, wherein the first of the 1st layer
The one side that cathode pole piece is coated with negative electrode active material coating is opposite with the 2nd layer of anode pole piece, remaining process and 1 phase of embodiment
Together, battery core 200 as shown in Figure 5 is obtained, battery core 200 only contains 1 first cathode pole piece 110.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that, there is no the first cathode pole in the battery core of comparative example 2
Piece, i.e., using two the first negative electrode tabs in two the second negative electrode tabs difference alternate embodiment 1, as shown in fig. 6, battery core 300 by
Second cathode pole piece 140 is alternately stacked with anode pole piece 120, the second adjacent cathode pole piece 140 and anode pole piece 120
Equipped with diaphragm 130.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 1, the difference is that, fire retardant is added to negative electrode active and applied by comparative example 3
In material, after coating drying, fire retardant is present in negative electrode active material coating.It should be noted that entire battery core in fire retardant and
Its dosage is same as Example 1, i.e., fire retardant used in the first cathode pole piece of head and the tail two panels is uniformly distributed in comparison in embodiment 1
In the negative electrode active material coating of 5 cathode pole piece of example.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 1, the difference is that, fire retardant used in embodiment 1 is added to just
In the reactive coating of pole, after coating drying, fire retardant is evenly distributed in positive electrode active materials coating.
Performance test
1, security performance is tested
3 hours are stood after battery core prepared by above-described embodiment 1~7 and comparative example 1~4 is completely filled with 0.7C at normal temperature,
Then 140 DEG C of hot tank tests are carried out according to GB/T 31485-2015, test result is shown in Table 1.It should be noted that being tested in table
As a result " passing through " expression battery core is not on fire after heating does not explode, and "/" can not be carried out because of battery catches fire in test process
Inner walkway after heating.
Table 1
As can be seen from Table 1, compared to comparative example 3, (i.e. conventional method adds fire retardant in negative electrode active coating
In), the security performance of battery core can be improved in the method for the embodiment of the present invention, effectively prevents battery core and loses under hot abuse condition
Effect；Compared to comparative example 1~4, the embodiment of the present invention by folded core outermost layer negative electrode tab coat anti-flaming dope formed it is fire-retardant
Coating not will increase the internal resistance of cell, can guarantee the high rate performance and cycle performance of battery.And as comparative example 3 and 4 adds fire retardant
Enter into positive or negative pole active material coating, the internal resistance of battery is then multiplied.Examples 1 to 3 and 6~7 with embodiment 4 and
5 compare, it can be seen that contain inorganic fire retardants and organic fire-retardant in flame retardant coating simultaneously, can preferably improve fire-retardant effect
Fruit.
2, electrochemical property test
Battery core prepared by Examples 1 to 3 and comparative example 2~4 is subjected to low temperature, room temperature discharge-rate performance and normal temperature circulation
Performance test, and recording capacity conservation rate, the results are shown in Table 2.
Table 2
As shown in Table 2, the high rate performance and cyclicity of the embodiment of the present invention 1~3 and comparative example 2 (conventional batteries)
Can quite, and there is different degrees of deterioration in the high rate performance and cycle performance of 4 battery core of comparative example 3 and comparative example.
To sum up, by the security performance test result of table 1 and 2 electrochemical property test result of table it is found that the embodiment of the present invention
Method the security performance of battery not only can be improved, but also will not influence internal resistance and the chemical property of battery core.
3, lancing test
3 hours are stood after completely being filled under Examples 1 to 7 and the battery core room temperature of the preparation of comparative example 1~4 with 0.7C, is then pressed
Lancing test is carried out according to GB/T 31485-2015, counts the flame out time during each group Cell Experimentation An, test result is shown in
Table 3.
Table 3
By the test result of table 3 it is found that the present invention can be obviously improved ability of the battery by lancing test, wherein according to reality
4 groups of battery percent of pass for applying the method test of example 1 are 100%, and in embodiment 3, due to being homogenized technique anti-flaming dope,
Slurry dispersion is poor, therefore battery, after needle thorn kindling, the time phase difference of fray-out of flame is larger.And by comparing 1 He of embodiment
Embodiment 4~5 using inorganic and organic fire-retardant is compound than any fire retardant effect is used alone it is found that get well.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of battery core, which is characterized in that including being located at first cathode pole piece of two panels in outside, being located at the first cathode described in two panels
Anode pole piece between pole piece, and the diaphragm between first cathode pole piece and the anode pole piece；
First cathode pole piece includes the first negative current collector, the cathode work on one surface of the first negative current collector
Property material coating, and the flame retardant coating on another surface of the first negative current collector, each first cathode pole piece
On the negative electrode active material coating be oppositely arranged with the anode pole piece；Wherein, the raw material of the flame retardant coating includes
Fire retardant, antisettling agent, bonding agent and surfactant.
2. battery core according to claim 1, which is characterized in that the battery core further includes the second cathode pole piece, and described second
Cathode pole piece includes the second negative current collector and the negative electrode active material that is respectively arranged on two surface of the second negative current collector
Coating；
The quantity of the anode pole piece is n, and n is the integer more than or equal to 2；The quantity of second cathode pole piece is n-1；
Second cathode pole piece described in anode pole piece described in n piece and n-1 piece is arranged alternately, and the adjacent anode pole piece and described
Diaphragm is equipped between second cathode pole piece.
3. battery core according to claim 1, which is characterized in that the fire retardant is selected from inorganic fire retardants and organic fire-retardant
At least one of；
Wherein, the inorganic fire retardants is selected from encapsulated red phosphorus, polyphosphoric acid amine, melamine polyphosphate expansion type flame retardant and answers
At least one of mould assembly inorganic fire retardants；The organic fire-retardant is selected from 2,2-, and bis- ((4- Phenoxyphenyl phosphine oxide)-is to ammonia
Yl benzoic acid) propane, bis- (2- carboxy ethyl) phosphonic acids, double-(p- benzoic acid)-phenyl-phosphamide, N- benzoic acid-(ethyl-N-
Benzoic acid formamide) phosphamide, poly- N- aniline-phenyl-phosphamide, 2- (Dimethyl phosphate) -4,6 (p-aminobenzoic acid) -
S-triazine, high fluorine carbonic ester, phosphate flame retardant, six benzene oxygen rings, three phosphonitrile, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
At least one of oxide and phosphine esters fire retardant.
4. battery core according to claim 3, which is characterized in that the fire retardant is inorganic fire retardants and organic fire-retardant
Mixture.
5. battery core according to any one of claims 1 to 4, which is characterized in that the bonding agent be selected from aqueous styrene-butadiene latex,
At least one of Kynoar, sodium carboxymethylcellulose, polytetrafluoroethylene (PTFE) and polyethylene glycol oxide；And/or
The antisettling agent is selected from nonionic polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty acid sulfate and polyglycol ether
At least one of；And/or
The surfactant be selected from alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, aliphatic acid polyethenoxy acid,
At least one of fatty acid methyl ester ethoxylate and the ethylene oxide adduct of polypropylene glycol.
6. a kind of battery pole piece, which is characterized in that the active material including collector, on one surface of collector applies
Layer, and the flame retardant coating on another surface of the collector；The raw material of the flame retardant coating includes fire retardant, anti-settling
Agent, bonding agent and surfactant.
7. a kind of preparation method of battery pole piece, which comprises the following steps:
Collector is provided；
Active material coating is coated on a surface of the collector, forms active material coating；
The raw material of flame retardant coating is uniformly mixed with solvent, obtains anti-flaming dope, the anti-flaming dope is coated in the afflux
On another surface of body, after dry, the flame retardant coating is formed；Wherein, the raw material of the flame retardant coating includes fire retardant, resists and sink
Depressant prescription, bonding agent and surfactant.
8. preparation method according to claim 7, which is characterized in that mix the raw material of flame retardant coating with solvent described
In uniform step, first the solvent, the antisettling agent, the bonding agent and the surfactant are mixed, stirred evenly, is obtained
It is mixed to the first mixing；First mixed liquor and the fire retardant are mixed again, stirred evenly under vacuum conditions.
9. according to claim 7 preparation method, which is characterized in that the fire retardant, the solvent, the antisettling agent,
The weight ratio of the bonding agent and the surfactant is (6.5~8.9): (5.8~7.7): (0.05~0.08): (0.03
~0.09): (0.005~0.01)；
The solvent is selected from least one of dimethyl carbonate, deionized water, N-Methyl pyrrolidone.
10. a kind of battery, which is characterized in that the battery pack described in any item battery cores containing Claims 1 to 55.
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